Bactericidal quaternary ammonium derivatives of indene

ABSTRACT

A method of microbiocidally treating a surface or treating hard water which comprises applying to the surface or admixing with the water microbiocidal quaternary ammonium derivatives of indene, at least some of which retain a high degree of their microbiocidal activity in hard water, the quaternary nitrogen having a long chain alkyl of eight to 18 carbon atoms, but preferably 12 to 14 carbon atoms and two lower alkyl chains of 1 to 4 carbon atoms attached thereto.

United States Patent Shay et al. [451 July 18, 1972 54] BACTERICIDAL QUATERNARY [56] References Cited AMMONIUM DERIVATIVES OF INDENE UNITED STATES PATENTS Inventors: Edward Grim y Belle Mead; Edward 2,676,986 4/1954 Wakeman et al. ..260/567.6

A. Tavss, Jersey City, both of NJ. Primary Examiner Alben T Meyers [73] Assignee: Mlllmaster Onyx Corporation, New York, Assistant Examiner--Frederick E. Waddell N.Y. Attorney-Arthur A. Jacobs [22] Filed: April 9, 1971 [57] ABSTRACT [21] Appl' 132910 A method of microbiocidally treating a surface or treating Related Application Data hard \vater which comprises applying to the surface or admixmg with the water nucrobiocldal quaternary ammonium Dlvlslon 0f 357,573, P 12, 1969, Pat derivatives of indene, at least some of which retain a high 3,636,115 degree of their microbiocidal activity in hard water, the quaternary nitrogen having a long chain alkyl of eight to 18 [52] U.S. Cl ..424/329 carbon atoms, but f bl 12 to 14 carbon mums and two lllt- 9/20 lower alkyl chains of l to 4 carbon atoms attached thereto. [58] Field of Search ..424/329 2 Claims, No Drawings This is a division of application Ser. No. 857,573, filed Sept. 12,1969, now U.S. Pat. No. 3,636,l 15.

This invention relates to a new class of microbiocidally active quaternary ammonium compounds, and it particularly relates to quaternary ammonium compounds derived from indene.

Many quaternary ammonium compounds have heretofore been known which were very effective microbiocidal agents. However, most of these prior compounds were found to lose a large part of their microbiocidal effectiveness when subjected to dilution with hard water. The compounds of the present invention are quaternary ammonium derivatives of indene wherein the quaternary nitrogen has a long chain of eight to 18 carbon atoms and also has two lower alkyls of one to four carbon atoms attached thereto. These compounds are highly microbiocidal. Furthermore, those of these compounds which have a long chain of 12 to l4 carbon atoms have been found to be among the relatively few quaternaries which are not only highly microbiocidal but which are not deleteriously affected by hard water.

The term hardwater is generally used to describe water having at least about 75 ppm. of calcium carbonate or equivalent salts. However, naturally occurring water may, and usually does contain such salts in an amount running up to several hundred ppm.

in accordance with the present invention, quaternary ammonium derivatives of indene may be prepared through hydrogenation, chloromethylation and reaction with tertiary amines as set forth in the following reaction.

CIIzCl In the above reaction, R is an alkyl group of between 12 and 14 carbon atoms, while R and R" are lower alkyls of one to four carbon atoms.

lndene is well known and widely used as a monomer for the preparation of commercial resins. It occurs in the solvent naphtha cuts of coal tar distillates. It is, therefore, an inexpensive and readily accessible raw material for chemical synthesis. This makes the present invention even -more valuable because other quaternary ammonium compounds which may have some of the same properties require the use of expensive and difficultly obtainable materials.

The following examples are illustrative of the present invention, but are not intended as limitations thereof except as claimed:

EXAMPLE I discharged and filtered to remove the catalyst. Methanol and forerun up to 170 C. were removed by distillation, and material boiling at l70l76 C. was taken as the product (650 grams). Although the pressure used here was 60 psi., it has been found that a pressure as high as about 500 psi. may be used with the same result.

EXAMPLE [I To a stirred mixture containing 590 grams of indan from Example I, 507 cc of 37 percent formaldehyde and l,060 cc of conc. HCl, was added 695 cc of conc. sulfuric acid over seven hours. The temperature was held at 60 C. for this period. Stirring was continued for 20 hours. The reaction mixture was then poured into ice'water and extracted with ethyl ether. The ether layer was washed twice with 5 percent sodium bicarbonate and once with water. It was then dried overnight over anhydrous sodium sulfate, filtered and then distilled.

Fractions having a boiling point of 120-l40 C. at 8-l0 mm were combined to give 420 grams of chloromethyl indan.

EXAMPLE Ill Chloromethyl indan was reacted with several alkyl dimethyl The chloride and amine were weighed into a 50 ml round bottom flask and an equal weight of isopropyl alcohol added. The mix'was refluxed on a steam bath overnight giving percent conversion to alkyl dimethyl indanyl methyl ammonium chloride in each case.

EXAMPLE IV The products of Example III were evaluated for Hard Water Tolerance using the AOAC Germicidal and Detergent Sanitizers test method procedure No. 5023 with E. coli ATCC No. 11229.

The results were as follows:

Product HWT (I) Decyl dimethyl indanyl methyl ammonium chloride 200 (2) Dodecyl dimethyl indanyl methyl ammonium chloride l I00 (3) Tetradecyl dimethyl indanyl methyl ammonium chloride 700 (4.) 70% 2)/30% 3) 900 The Phenol Coefficient for (2) vs. S. aureus was determined to be 830; vs. S. typhasa 780.

EXAMPLE V Product HWT (5) Decyl diethyl indanyl methyl ammonium chloride 300 (6) Dodecyl diethyl indanyl methyl ammonium chloride 700 (7) Dodecyl dimethyl indanyl methyl ammonium chloride 1 I00 700 (8) Tetradecyl dimethyl indanyl methyl ammonium chloride By comparing results obtained using products (2) and (3) from Example IV with products (7) and (8) above, it can be seen that the products derived from indan derived from a commercial source without extensive purification are equivalent to those obtained using highly purified indan. This is significant because it obviates the necessity for expensive and time-consuming purification.

The results of microbiocidal activity, as indicated above, show unexpectedly excellent hard water tolerance of the products of this invention since even the adjacent decyl compounds are significantly inferior in this respect.

Instead of chlorine, other halogens such as bromine and iodine may be used as the anion.

The invention claimed is:

1. A method of bactericidally treating a surface which comprises applying thereto a bactericidally effective amount of a compound of the formula:

wherein R is an alkyl group of eight to l8 carbons, R and R" are lower alkyls ofone to four carbons, and X is a halogen.

2. A method of treating hard water to make it bactericidal which comprises treating said water with a bactericidally cf fective amount of a compound of the formula:

wherein R is an alkyl group of eight to 18 carbons, R and R" are lower alkyls of one to four carbons, and X is a halogen. 

2. A method of treating hard water to make it bactericidal which comprises treating said water with a bactericidally effective amount of a compound of the formula: 